Stabilized non-medical fungicidal, bactericidal and algicidal composition

ABSTRACT

A halocyanoacetamide compound having the formula: ##STR1## wherein X is a halogen such as Cl, F, Br and I; Y represents a halogen such as chlorine, fluorine, bromine and iodine or hydrogen atom; and 
     R represents a hydrogen atom or a lower alkyl group containing from 1 to 8 carbon atoms, is stabilized with an organic carboxylic acid or a diol.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a stabilized non-medicinal fungicidal,bactericidal and algicidal composition which comprises ahalocyanoacetamide compound.

2. Description of the Prior Art

Non-medicinal fungicidal and algicidal compositions are useful forinhibiting the growth of fungi, bacteria, yeasts, algae, and the like inindustrial waters, such as the effluent from paper mills, or industrialcooling water; in cooling water for air-conditioners or in othermaterials such as metal processing lubricant oils, latex emulsions,aqueous emulsions, paper, wood, plywood, paints, pastes, pulps, fibers,and the like. However, the unlimited proliferation of such amicroorganism can cause a decrease in product quality of can causeproduct damage. It can also result in long operation shutdowns or canotherwise cause severe economic loss.

The control of the proliferation of the microorganism in industrialwaters is especially important in those systems that use large waterrecirculation systems, since such systems can become virtual breedinggrounds for the growth of a wide variety of organisms. As the watersbecome increasingly contaminated, disposal becomes a worsening problembecause discharge into waterways could cause pollution of rivers or thesea. Moreover, the unrestricted growth of microorganisms can causeclogging of pipes or can frustrate heat-exchange mechanisms due to thebuild-up of fungi, or bacteria, generally called slime and algae. Slimeformed in an important part of apparatus, such as in a white water tank,a riffler wall or a screen in the paper and pulp industry can stainproducts thereby decreasing quality. Slime present in papermanufacturing can also cause tearing of the paper in the high speedprocessing machines. Such microorganism-caused difficulties can alsooccur in lubricant emulsion recycling systems commonly used in metalprocessing. In these systems, the proliferation of fungi or bacteria canresult in rotting of the emulsion. In many other industries as well,such as those engaged in the production of paints, latex emulsions,fiber pastes, plywoods, etc., the proliferation of fungi or bacteria canbe quite deleterious. Consequently, a need exists for a technique forpreventing or controlling the proliferation of these microorganisms.

SUMMARY OF THE INVENTION

Accordingly, it is one object of this invention to provide a stabilizednon-medical fungicidal, bactericidal and algicidal composition involvingthe prevention of difficulties caused by proliferation of theseorganisms in industrial wastes.

It is another object of this invention to provide a process forpreparing a stabilized non-medical fungicidal, bactericidal andalgicidal composition. These and other objects of this invention, aswill hereinafter become more readily apparent from the ensuingdiscussion, have been attained by providing a composition whichcomprises as active ingredient a halocyanoacetamide having the formula(I) ##STR2## wherein X represents a halogen atom such as chlorine,fluorine, bromine and iodine and Y is such a halogen or hydrogen atom;and R represents a hydrogen atom or a lower alkyl group, containing from1 to 8 carbon atoms and stabilizer of an organic carboxylic acid such asa dicarboxylic acid, an hydroxy carboxylic acid and a monocarboxylicacid and the like, or a diol containing up to 14 carbon atoms. Thestabilized non-medicinal fungicidal, bactericidal and algicidalcomposition preferably comprises an halocyanoacetamide having theformula (I) and a haloacetic ester having the formula (II) ##STR3##wherein Z represents a halogen such as fluorine, chlorine, bromine andiodine and A represents an alkylene or alkenylene group containing from1-8 carbon atoms and a stabilizer of an organic carboxylic acid or adiol.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Suitable halocyanoacetamides of the formula (I), includemonochlorocyanoacetamide, monobromocyanoacetamide,dichlorocyanoacetamide, dibromocyanoacetamide,N-methyldibromocyanoacetamide, or the like. Suitable haloacetic estersof the formula (II) include 1,2-bis(bromoacetoxy) ethane,1,2-bis(bromoacetoxy) propane, 1,2-bis(chloroacetoxy) ethane,1,4-bis(bromoacetoxy)-2-butene. The combination of dibromocyanoacetamideand 1,4-bis(bromoacetoxy)-2-butene provides very high microbiocidal andalgicidal effects. Suitable organic carboxylic acids and diols used forstabilizing compositions comprising a halocyanoacetamide having theformula (I) and a haloacetic ester of the formula (II), include organicacids such as succinic acid, salicylic acid, oxalic acid, α-tartaricacid, phthalic acid, fumaric acid, propionic acid, maleic acid, malonicacid, malic acid, bromoacetic acid, lactic acid, citric acid, formicacid, oleic acid and the like; and diols such as ethyleneglycol,1,2-propanediol, 1,3-propanediol, 1,2-dihydroxybutane,2,3-dihydroxybutane, 1,3-dihydroxybutane, 1,4-dihydroxy-2-butyne,1,4-dihydroxy-2-butene, 1,5-dihydroxypentane, 1,6-dihydroxyhexane,2,5-dihydroxyhexane, 1,7-dihydroxyheptane, 2,5-dihydroxy-(3)-hexene andthe like. These stabilizers can be used for increasing the stability ofthe halocyanoacetamide used alone or in combination with a haloaceticester. It is especially preferred for stabilization to use lactic acidor citric acid as the organic carboxylic acid or 1,4-dihydroxy-2-buteneor .Badd..[.1,4-hydroxybutane.]. .Baddend..Iadd.1,4-dihydroxybutane.Iaddend.as the diol. The amount of the organic carboxylic acid or thediol employed is usually 0.01-10 wt. %, preferably 0.1-5 wt. % relativeto the amount of the composition containing the halocyanoacetamidehaving the formula (I).

Additionally, it is preferred to use the halocyanoacetamide of formula(I) and the haloacetic ester of formula (II) in the form of an emulsionby adding a desirable solvent and a desirable surfactant. Suitablesolvents include 1,1,1,-trichloroethane, xylene, polyols, ketones andthe like. The preferred amount of the solvent is that sufficient todissolve the active ingredients. When a surfactant is added, it issometimes unnecessary to add a solvent since many surfactants can servethe purpose. The amount of the surfactant to be added depends upon thenature of the composition and is usually 0.01-20 wt. %, preferably 0.1-5wt. %. The active ingredients can also be used in the form of a wettablepowder by combining them with a mineral carrier such as bentonite, whiteclay, silica and the like, and with a surfactant. If the water to betreated is alkaline, it is preferred to add an acid to the water inorder to neutralize it or to the composition itself.

When the water has an alkaline pH, the halocyanoacetamide of formula (I)is unstable by itself suffering a decrease in its effect within a shorttime. Accordingly, it has been difficult to obtain a desirablefungicidal, bactericidal and algicidal effect. Addition of an alkalimetal halide has been proposed to improve the effect of thehalocyanoacetamide. However, the results are unsatisfactory as shown inthe tests described hereinafter. On the other hand, the haloaceticesters having the formula (II) have known activity for inhibiting thegrowth of fungi, bacteria, yeasts, algae, and the like. However, it isnecessary to use these agents in high concentration. Accordingly, whenused for slime control, there are significant disadvantages with respectto cost and capability for maintaining the effectiveness of thecomposition. As can clearly be seen from the above discussion, bothcompounds (I) and (II) have known disadvantages which make theprobability for the successful use of either separately as an industrialmicrobiocide and algicide marginal at best. It is therefore quitesurprising that the present inventors have now found that thecombination of compounds (I) and (II) provides excellent microbiocidaland algicidal effects when formulated in a ratio of compound I: compoundII; of 1:0.1-10, preferably 1:0.2-4, even in low concentrations.However, even in that combination, the halocyanoacetamide of formula (I)is disadvantageously unstable. But as indicated above, when stabilizedby combination with an organic carboxylic acid or a diol, thehalocyanoacetamide or formula (I) maintains its activity for a longperiod of time. Thus, when the compound (I) is combined with thehaloacetic ester of formula (II), the synergistic effect mentioned abovecan be advantageously maintained.

The microbiocidal and algicidal compositions of the present inventionare effective against a wide variety of fungi, such as Aspergillusniger, Penicillium steckii, Trichoderma, Geotrichum, and Candidum;bacteria, such as Aerobacter aerogenes or Bacillus subtilis; and thelike. They can be used in low concentrations. (In such concentrations,each of the compounds would not impart fungicidal effects if used as inthe prior art.) Consequently, the growth of noxious microorganisms inindustrial waters can be completely inhibited with relatively smallamounts of the composition. The composition of the present invention istherefore ideal for use as a slime control agent for inhibiting theproliferation of microorganisms, such as fungi, bacteria, yeasts, algaeand the like, in recycled water systems, such as those used in paper orpulp mills and in cooling towers and the like. When the compounds (I)and (II) are combined in the above-mentioned ratios, the fungi,bacteria, yeasts and algae which cause the slime can be effectivelyinhibited in using only a low concentration of active ingredients.

Having generally described the invention, a more complete understandingcan be obtained by reference to certain specific examples tests andexperiments which are included for purposes of illustration only and arenot intended to be limiting unless otherwise specified. In theseexamples, the terms "part" designates "parts by weight".

EXAMPLE 1

15 parts of dibromocyanoacetamide, 15 parts of1,4-bis(bromoacetoxy)-2-butene, 43.5 parts of polyethyleneglycol (M.W.200), 25 parts of 1,1,1-trichloroethane, 0.7 part of polyoxyethylenenonylphenyl ether, 0.3 part of calcium dodecylbenzenesulfonate and 0.5part of 1,4-dihydroxy-2-butene as a stabilizer were mixed to form anemulsifiable concentrate.

EXAMPLE 2

15 parts of dibromocyanoacetamide, 15 parts of1,4-bis(bromoacetoxy)-2-butene, 43.5 parts of polyethyleneglycol (M.W.200), 25 parts of 1,1,1-trichloroethane, 0.7 part of polyoxyethylenenonylphenyl ether, 0.3 part of calcium dodecylbenzensulfonate and 0.5part of 1,4-dihydroxybutane as a stabilizer were mixed to form anemulsifiable concentrate.

EXAMPLE 3

15 parts of dibromocyanoacetamide, 15 parts of1,4-bis(bromoacetoxy)-2-butene, 1.7 parts of polyoxyethylene nonylphenylether, 0.3 part of calcium dinaphthylmethanedisulfonate, and 0.5 partsof 1,4-dihydroxybutane as a stabilizer and 67.5 parts of diatomaceousearth were mixed and crushed to form a wettable powder.

EXAMPLE 4

15 parts of dibromocyanoacetamide, 15 parts of1,4-bis(bromoacetoxy)-2-butene, 43.5 parts of ethyleneglycol, 25 partsof 1,1,1-trichloroethane, 0.7 part of polyoxyethylene nonylphenyl ether,0.3 part of calcium dodecylbenzenesulfonate and 0.5 part of lactic acidas a stabilizer were mixed to form an emulsifiable concentrate.

EXAMPLE 5

15 parts of dibromocyanoacetamide, 5 parts of1,4-bis(bromoacetoxy)-2-butene, 53.5 parts of polyethyleneglycol (M.W.200), 25 parts of 1,1,1-trichloroethane, 0.7 part of polyoxyethylenenonylphenyl ether, 0.3 part of calcium dodecylbenzenesulfonate and 0.5part of 1,2-dihydroxyethane (stabilizer) were mixed to form anemulsifiable concentrate.

EXAMPLE 6

8 parts of dibromocyanoacetamide, 28 parts of1,4-bis(bromoacetoxy)-2-butene, 27.5 parts of polyethyleneglycol (M.W.200), 35 parts of 1,1,1-trichloroethane, 0.7 part of polyoxyethylenenonylphenyl ether, 0.3 part of calcium dodecylbenzenesulfonate and 0.5part of 1,7-dihydroxyheptane (stabilizer) were mixed to form anemulsifiable concentrate.

EXAMPLE 7

20 parts of dibromocyanoacetamide, 78.5 parts of polyethyleneglycol(M.W. 200), 0.7 part of polyoxyethylene nonylphenyl ether, 0.3 part ofcalcium dodecylbenzenesulfonate and 0.5 parts of 1,4-dihydroxy-2-butene(stabilizer) were mixed to form an emulsifiable concentrate.

EXAMPLE 8

20 parts of dibromocyanoacetamide, 78.5 parts of polyethylene glycol(M.W. 200), 0.7 part of polyoxyethylene nonylphenyl ether, 0.3 part ofcalcium dodecylbenzenesulfonate and 0.5 part of 1,4-dihydroxybutane(stabilizer) were mixed to form an emulsifiable concentrate.

EXAMPLE 9

20 parts of dibromoacetamide, 1.7 parts of polyoxyethylene nonylphenylether, 0.3 part of calcium dodecylbenzenesulfonate, 3 parts of silicagel (white carbon No. 80), 74.5 parts of diatomaceous earth and 0.5 partof citric acid (stabilizer) were mixed and crushed to form a wettablepowder.

TEST 1

20 parts of dibromocyanoacetamide, 0.7 part of polyoxyethylenenonylphenyl ether, 0.3 part of calcium dodecylbenzenesulfonate and 78.5parts of polyethyleneglycol and the stabilizer shown in Table 1 weremixed to form emulsifible concentrates. The concentrates were stored at40° C for 20 days in a cylinder. Thereafter, the stability of thecompositions was measured by biological tests using the culture mediumcloudiness method. The results are shown in Table 1.

                  Table 1                                                         ______________________________________                                                  Con-                 Value                                                    cen-    Value of     40° C,                                                                       Decompo-                                 Stabilizer                                                                              tration dibromoacetamide                                                                           20 days                                                                             sition rate                              ______________________________________                                        succinic acid                                                                           0.5     20.6         19.3  6.3                                      oxalic acid                                                                             0.5     20.0         19.0  5.0                                      maleic acid                                                                             0.5     20.1         19.2  4.5                                      lactic acid                                                                             0.5     21.0         30.3  3.3                                      citric acid                                                                             0.5     20.8         20.2  2.9                                      1,4-dihydroxy-                                                                          0.5      20.00       19.9  3.4                                      butane                                                                        1,4-dihydroxy-                                                                          0.5     20.4         19.9  2.5                                      butene                                                                        Reference                                                                     sodium    0.5     20.3         18.5  8.9                                      iodide                                                                        none      --      21.0         15.9  24.3                                     ______________________________________                                    

TEST 2

15 parts of dibromoacetamide, 15 parts of1,4-bis(-bromoacetoxy)-2-butene, 0.7 part of polyoxyethylene nonylphenylether, 0.3 part of sodium dodecylbenzenesulfonate, 43.5 parts ofpolyethyleneglycol (M.W. 200 ), 25 parts of 1,1,1-trichloroethane and0.5 part of the stabilizers shown in Table 2 were mixed to formemulsifiable concentrates. The concentrates were stored at 40° C for 20days in a cylinder. Thereafter, the stability of the compositions weremeasured by biological tests using the culture medium cloudiness method.The results are shown in Table 2.

                  Table 2                                                         ______________________________________                                                             Value of  Value                                                      Concent- dibromo-  40° C                                                                        Decompo-                                 Stabilizer  ration   acetamide 20 days                                                                             sition rate                              ______________________________________                                        succinic acid                                                                             0.5%     14.2      13.2  7.0                                      salicylic acid                                                                            "        14.8      13.6  8.1                                      oxalic acid "        14.6      13.0  11.0                                     α-tartaric acid                                                                     "        14.6      13.4  8.2                                      phthalic acid                                                                             "        14.4      13.4  6.9                                      fumaric acid                                                                              "        14.2      13.0  8.5                                      propionic acid                                                                            "        14.2      13.5  4.9                                      maleic acid "        14.3      13.3  7.0                                      malonic acid                                                                              "        14.3      13.3  7.0                                      lactic acid "        14.2      14.3  6.3                                      malic acid  "        14.8      14.0  5.4                                      bromoacetic acid                                                                          "        14.3      12.6  11.9                                     lactic acid "        14.6      14.2  2.7                                      formic acid 0.5%     14.5      13.6  6.2                                      oleic acid  "        14.6      13.9  4.8                                      citric acid "        14.7      14.4  2.0                                      1,2-dihydroxy-                                                                butane      "        14.3      13.1  8.4                                      1,3-dihydroxy-                                                                butane      "        14.6      13.2  9.6                                      1,4-dihydroxy-                                                                butane      "        14.5      14.1  2.8                                      2,3-dihydroxy                                                                 butane      "        14.5      13.6  6.2                                      1,4-dihydroxy-2-                                                              butyne      "        14.3      13.2  7.7                                      1,4-dihydroxy-2-                                                              butyne      "        14.8      14.2  4.1                                      Reference                                                                     sodium iodate                                                                             "        14.7      13.0  9.1                                      none        --       14.2        9.1 35.9                                     ______________________________________                                    

TEST 3

15 parts of bromocyanoacetamide, 15 parts of1,4-bis(bromoacetoxy)-2-butene, 0.7 part of polyoxyethylene nonylphenylether, 0.3 part of calcium dodecylbenzenesulfonate, 43.5 parts ofpolyethyleneglycol (M.W. 200), 25 parts of 1,1,1-trichloroethane and 0.5part of the stabilizer shown in Table 3 were mixed to form emulsifiableconcentrates. The concentrates were stored at 40° C for 20 days, andthen the amount of 1,4-bis(bromoacetoxy)-2-butene was determined by theGLC method. The results are shown in Table 3.

                  Table 3                                                         ______________________________________                                                          Value of 1,                                                           Con-    4-bis-       Value                                                    cent-   (bromoacetoxy)-                                                                            40° C                                                                        Decompo-                                 Stabilizer                                                                              ration  2-butene     20 days                                                                             sition rate                              ______________________________________                                        succinic acid                                                                           0.5%    14.8         14.6  1.4                                      salicylic acid                                                                          "       14.6         14.3  2.1                                      oxalic acid                                                                             "       15.0         14.8  1.3                                      α-tartaric acid                                                                   "       15.1         14.6  3.3                                      phthalic acid                                                                           "       15.0         14.3  4.7                                      fumaric acid                                                                            "       14.9         14.7  1.3                                      propionic acid                                                                          "       14.3         13.8  3.5                                      maleic acid                                                                             "       15.0         14.4  4.0                                      malonic acid                                                                            "       14.9         14.7  1.3                                      lactic acid                                                                             "       14.9         14.0  6.0                                      malic acid                                                                              "       15.1         14.7  2.6                                      bromoacetic                                                                   acid      "       15.2         14.7  3.3                                      lactic acid                                                                             "       14.7         14.5  1.4                                      formic acid                                                                             0.5%    14.9         14.3  4.0                                      oleic acid                                                                              "       14.7         14.3  2.7                                      citric acid                                                                             "       14.8         14.8  0                                        1,2-dihydroxy-                                                                butane    "       14.8         14.6  1.4                                      1,3-dihydroxy-                                                                butane    "       15.0         14.6  2.7                                      1,4-dihydroxy-                                                                butane    "       15.0         15.0  0                                        2,3-dihydroxy-                                                                butane    "       15.1         14.7  2.6                                      1,4-dihydroxy-2-                                                              butyne    "       15.2         14.6  3.9                                      1,4-dihydroxy-2-                                                              butyne    "       14.8         14.7  0.7                                      Reference                                                                     sodium iodate                                                                           "       14.8         14.1  4.7                                      none      --      14.3         10.3  28.0                                     ______________________________________                                    

EXPERIMENT 1

Aerobacter aerogenes IAM 1102 which typically grows in a water system,was cultured in a broth liquid medium by shaking for 24 hours, and thenwas diluted 1,000 times. 1 ml of the diluted solution containingAerobacter aerogenes was added to 18 ml of a fresh broth liquid mediumcontained in several 50 ml conical flasks closed with sterilized cotton.1 ml portions of the solutions having the active ingredientconcentrations as defined in Table 4, were added to the flasks. Theflasks were shaken in a bath kept at 28° C. After 5, 15, 30, 90 and 180minutes from the addition of the active ingredient, the concentrationsof Aerobacter aerogenes in each broth liquid medium was measured todetermine the fungicidal effects of the active ingredient. The resultsare shown in Table 4.

The compositions used for the experiments were as follows.

No. 1: Example 4 composition

No. 2: Example 5 composition

No. 3: Example 6 composition

No. 4: 40% dibromocyanoacetamide emulsifiable concentrate

No. 5: 30% dibromocyanoacetamide + 20% sodium iodide emulsifiableconcentrate

No. 6: 60% 1,4-bis(bromoacetoxy)-2-butene

No. 7: none

                  Table 4                                                         ______________________________________                                                Conc. of                                                                      active    Time for contacting active ingredient                       Composi-                                                                              ingredient                                                                              (number of bacteria N/ml)                                   tion    (ppm)     10 min  30 min.                                                                             90 min.                                                                              180 min.                               ______________________________________                                        No. 1   6+  6     4,000   200   10     0                                      No. 2   9 + 3     3,500   600   50     10                                     No. 3   2.6 + 9.1 6,000   800   100    10                                     No. 4   15        28,000  74,000                                                                              82,000 100,000                                No. 5   15 + 10   28,000  68,000                                                                              50,000 68,000                                 No. 6   20        100,000 98,000                                                                              90,000 310,000                                No. 7   --        520,000 680,000                                                                             1,100,000                                                                            1,300,000                              ______________________________________                                    

Compound (I) or (II) when used alone with no stabilizer was noteffective for inhibiting the growth of Aerobacter aerogenes inconcentrations of 15-20 ppm. However, the combination of the twocompounds imparted unexpectedly high fungicidal effects at the sameconcentrations.

EXPERIMENT 2

The growth inhibition concentrations of the compositions in the presentinvention as measured by the agar dilution method in a broth liquidmedium (a pH of 7.5 in the case of bacteria and of 4.5 in the case offungi) were measured. The results are shown in Table 5. The activeingredients used in the tests are defined in Experiment 1.

                  Table 5                                                         ______________________________________                                                        Growth inhibition                                                             minimum concentration                                         Compo-          (active ingredient ppm)                                       sition          No. 1   No. 4   No. 5 No. 6                                   ______________________________________                                        Acrobacter aerogenes                                                                          6       100     100   75                                      Bacillus subtillis                                                                            6       100     100   50                                      Escherichia Coli                                                                              6        25      25   50                                      Pseudomonas aeruginosa                                                                        6        25      25   50                                      Aspergillus niger                                                                              12.5   200     200   100                                     Penicillium steckii                                                                           6       250     200   100                                     Trichoderma SP  6       200     200   150                                     Geotrichum candidum                                                                           6       150     150   75                                      ______________________________________                                    

As is clear from Table 5, compounds (I) or (II) are each much lesseffective when used alone with no stabilizer for the inhibition ofbacteria, as when used in combination. The combinations themselves arequite effective against microorganisms which cause difficulties forindustrial water systems and in industrial products, such as Aerobacteraerogenes, Bacillus subtilis, Escherichia coli, Pseudomonas aeraginosa,Aspergillus niger, Penicillium steckii, Trichoderma SP, Geotrichumcadidum.

EXPERIMENT 3 Fungicidal activites in white water under weak alkalineconditions

Into a 100 ml conical flask, was introduced 18 ml of white watercontaining 0.05-0.1% of pulp fibrils. The pH was adjusted to 8.1 and 2ml of a diluted solution of the combination of the present inventioncontaining concentrations of ingredients as shown in Table 6 were added.The mixture was continuously shaken at 30° C. After 30, 90 and 120minutes from the addition of the diluted solution, 1 ml of white waterwas extracted from each flask and was uniformly mixed with 16 ml of MWmedium and poured into a Petri dish having a diameter of 9 cm forsolidification. Each of the microorganisms was cultured at 28° For 48hours and the number in the colony in each Petri dish was counted todetermine the fungicidal effect of the active ingredients. The resultsare shown in Table 6. The compositions are the same as those ofExperiment 1.

                  Table 6                                                         ______________________________________                                               Conc. of                                                                      active                                                                        ingredient                                                                            Colony number in 1 ml of white water                           Composition                                                                            (ppm)     30 min.   90 min. 120 min.                                 ______________________________________                                        No. 1    12.5      2,800     380     10                                       No. 2    "         2,600     450     20                                       No. 3    "         3,100     420     10                                       No. 4    " "       650,000   130,000 6,600,000                                No. 5    "         460,000   110,000 3,600,000                                No. 6    "         1,000,000 840,000 420,000                                  No. 7    --        43,000,000                                                                              27,000,000                                                                            83,000,000                               ______________________________________                                    

EXPERIMENT 4

Cosmarium and Oscillatoria (algae) adhered onto a cooling tube werecollected and cultured. Compositions thereof 5, 10, 50, 100, 150 and 200ppm were prepared. The cultured Cosmarium or Oscillatoria was dippedinto a diluted solution of the active ingredient of this invention for 1hour, was removed and was also dipped into distilled water for 24 hours.The growth of Cosmarium or Oscillatoria was ascertained by separatingthe protoplasm thereof. The minimum effective concentration (ppm) of theactive ingredient of the algicide was determined. The results are shownin Table 7. The compositions are the same as those used in Experiment 1.

                  Table 7                                                         ______________________________________                                        Composition    No. 1     No. 4     No. 5                                      ______________________________________                                        Cosmarium      5         200        50                                        Oscillatoria   5         200       100                                        ______________________________________                                    

Having now fully described the invention, it will be apparent to one ofordinary skill in the art that many changes and modifications can bemade thereto without departing from the spirit or scope of the inventionas set forth herein.

What is claimed as new and desired to be secured by letters patent ofthe United States is:
 1. A stabilized microbiocidal composition whichconsists essentially of:a microbiocidally effective amount of ahalocyanoacetamide having the formula ##STR4## wherein X represents ahalogen atom; Y represents a halogen atom or a hydrogen atom; and Rrepresents hydrogen atom or a lower alkyl group containing from 1 to 8carbon atoms; a stabilizer of a diol selected from the group consistingof ethylene glycol, 1,2-propanediol, 1,3-propanediol,1,2-dihydroxybutane, 2,3-dihydroxybutane, 1,3-dihydroxybutane,.Iadd.1,4-dihydroxybutane, .Iaddend.1,4-dihydroxy-2-butyne,1,4-dihydroxy-2-butene, 1,5-dihydroxypentane, 1,6-dihydroxyhexane,2,5-dihydroxyhexane, 1,7-dihydroxyheptane and 2,5-dihydroxy-(3)-hexene,wherein the amount of stabilizer is 0.1 - 5 wt. % relative to the amountof halocyanoacetamide; and a solvent.
 2. A stabilized microbiocidalcomposition which consists essentially of:a microbiocidally effectiveamount of a halocyanoacetamide having the formula ##STR5## wherein Xrepresents a halogen atom; Y represents a halogen atom or a hydrogenatom; and R represents hydrogen atom or a lower alkyl group containingfrom 1 to 8 carbon atoms; a stabilizer of a diol selected from the groupconsisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol,1,2-dihydroxybutane, 2,3-dihydroxybutane, 1,3-dihydroxybutane,.Iadd.1,4-dihydroxybutane, .Iaddend.1,4-dihydroxy-2-butyne,1,4-dihydroxy-2-butene, 1,5-dihydroxypentane, 1,6-dihydroxyhexane,2,5-dihydroxyhexane, 1,7-dihydroxyheptane and 2,5-dihydroxy-(3)-hexane,wherein the amount of stabilizer is 0.1 - 5 wt. % relative to the amountof halocyanoacetamide; a solvent; and a haloacetic ester having theformula ##STR6## wherein Z represents a halogen atom; and A representsan alkenylene group containing up to 8 carbon atoms; wherein the ratioby weight of the halocyanoacetamide having the formula I to thehaloacetic ester having the formula (II) is 1 : 0.1 -
 10. 3. A method oftreating water to inhibit the growth of microorganisms, which comprisesadding a microbiocidally effective amount of the composition of claim 1to said water.
 4. A method of inhibiting the growth of microorganismswhich comprises contacting said microorganism with a microbiocidallyeffective amount of the composition of claim
 1. 5. A method forinhibiting the growth of slime in water which comprises adding amicrobiocidally effective amount of the composition of claim 1 into saidwater.
 6. A method of treating water to inhibit the growth ofmicroorganisms, which comprises adding a microbiocidally effectiveamount of the composition of claim 2 to said water.
 7. A method ofinhibiting the growth of microorganisms which comprises contacting saidmicroorganisms with a microbioligically effective amount of thecomposition of claim
 2. 8. A method for inhibiting the growth of slimein water which comprises adding a microbiocidally effective amount ofthe composition of claim 2 in said water.